Process for the production of carbon disulfide



Jan. 19, 1954 o. FOLKINS ErAL PRocEss FOR THE PRODUCTION 0F CARBON DxsuLFIDE 2 Sheets-Sheet 1 Filed DeCS.y 28, 1951 H. o. FoLKlNs ETAL 2,666,690

PROCESS FoR THE PRODUCTION oF CARBON DISULFIDE 2 sheets-sheet 2 ww t l Jan. 19, 1954 Filed nec. 28, 1951 Patented Jan. 19, 1954 PnooEssFoR THE PRODUCTION oF v CARBON DISULFIDE Hillis 0. Folkins and Elmer Miller, Crystal Lake, and Harvey Hennig, Cary, Ill., assignors to Food Machinery and Chemical Corporation, New York, N. Y., acorporation of Delaware.

ApplicationvDecember 28, 195.1, Serial No. .263,724

18 Claims.

1 The present invention is directed to a process for converting hydrocarbons to carbon disulfide yby reaction with sulfurv wherein a scavenging or agglomerating material is utilized to nulliiy the deleterious eiect of side reaction products.

It is known to prepare carbon disulfide by reaction of sulfur with various hydrocarbons under catalytic 'conditions 'at elevated temperatures and pressures. It is reported that hydrocarbons having one to three carbon atoms in the molecule 'are preferred for the reaction for economic reasons, although certain investigators show that unsaturated hydrocarbons and higher molecular weightr hydrocarbons may be satisfactorily used in the process. Because oi the complexity-of the reaction when using higher molecular weight hydrocarbon charge gases wherein there are produced various side reaction products, it is generally preferable to use meth- Iane or a gas comprising highV percentages of methane for the reaction. Experiments have in- .dicated that hydrocarbons containing two to Iive carbon atoms in the molecule are prone to yield deleterious side reaction products which contaminate the carbon disulfide product; cause severe catalyst decline and consequent vdrop in conversion, and contaminate the recycle sulfur, making its recovery for reuse more difiicult. -T-he ynatural gases containing 4 mole per cent ofrCs hydrocarbons and 1 mole per cent or more of C4 hydrocarbons have been designated as borderline charge gases for the carbon disulfide reaction since even these small amounts ofhydrocarbons of higher molecular weight than methane have beenrfound to cause Vsevere catalyst contamination and plugging of the reaction zone with tars and polymers.

p lNumerousl techniques have been developed for increasing the eiiciency of the reaction and the ease of product recovery. These include new catalysts, use of an excess of sulfur over the stoichiometric requirements, preheating the charge gas and' sulfur to reaction temperature orabove, and techniques for separating the carbon disulfide from the` excess sulfur and side reaction products. These improved techniques have greatly increased the amount of carbon disulfide which can bev obtained from a given amount Yof charge gas;UA However, in their practice it is not always i possible to conduct the 2 n. reaction under conditions that are kinetically optimum for each hydrocarbon gas. For example, in some instances the space velocities of the reactants through the reaction zone must be adjusted downward from optimum space velocities suitable for the particular reaction environment of hydrocarbon gas and operating conditions used, in order to obtain maximum yields per pass from the reactants. The alternates to lower space velocities are to increase temperature and hence corrosion diiiiculties or to operate' under high pressures. Generally, the use of higher space velocities lowers the extent of conversion. Too low a conversion level will interfere with product separation and recovery. By operating under conditions of lower space velocities, higher conversions to carbon disulfide may be maintained, but the process is more inefficient and productivity may be lower. Naturally, the use of excessive amounts of sulfur complicates the product purification steps and sulfur recovery.

The present process eliminates the above problems without sacrifice of any of thev advantages gained from the use of theabove mentioned techniques, and is based on the discovery that by removing the deleterious side reaction products as they are formed by use of an agglomerating materialpresent during the reaction, their eiiect upon the reaction is minimized and the sulfur content thereof is made recoverable. Removal of the side reaction products allows operation at. all times. under optimum reaction conditions for maximum yield per pass without complicating product recovery or sulfur recycle.` This is extremely advantageous in a reaction of this type wherethedeleterious effects of the sulfurcontaining sidereaction productsfincrease with time and the presence ,of even a small amount in the reaction zone is very detrimental.

Accordingly, it is the primary object of this invention to provide a process for producing carbon disulde by reaction of hydrocarbons with sulfur under conditions of maximum convertsion, with a minimum of influence from side reaction products and with little or no diiiiculty in product recovery or sulfur recycle.

A secondary object of` this invention is to provide a .process for the eiiicient and economic production of carbon disulfide from hydrocarbons that are prone to form vdeleterious sulfur- .have proved eiective. .struction include :aluminum coated steels, ire- .Iractory linings, and .other .types of :stainless steels. l

containing side reaction products wherein an agglomerating material, which may be catalytic or not, acts to remove these deleterious side reaction products from contact with the reactants before there has been an opportunity for them to lower the reaction emciency.

Another object of this invention is to take advantage of the unreacted sulfur content and the combined sulfur content within the effluent products, removed by the agglomerating material, to react 'with aprincipal byeproduct, hydrogen sulfide, .from `the reaction, thus 'reforming in usable condition sulfur which would .otherwise be lost.

Still another object of this inventionis toprovide a process for producing carbon `disulfide wherein an agglomerating material removes the tars, polymers, some of the excesssulfur, anilsulfur-carbon complexes for exidationito substantial amounts of sulfur dioxide, Whiehis'utilized" to react with. the hydrogen suld'e'byeproductito form elemental sulfur for reuserinrthe ...reaction Further objects and advantages of the invention will become apparent as the description thereof proceeds.

The term principalproducts fas =used'herein appliesto the carbon disuliide andhydrogen sul-'- fide which are `the normal Yproducts Ao thevco'rr.- plete reaction rof sulfur and charge gas. "The term sidereaction.products'wil1lbe usedto refer to Vthe Aproducts formed from Vthe-'incomplete sulfur oxidation of fthe carbon andhydrogen-content of the charge gas. These "include carbon 'hydrogen-sulfur complexes, 'sulfur-carbon complexes, tars, and coke 'above referred to.

In the accompanyingdrawingsjFigure"l shows 'one'typeofreactor for producing carbon disulde and a -system for loxidizing' thehydrogen sulii'de to elemental sulfur. `l'iefure'Zshovvs a'system'for separating carbon disulldefromhydrogen sulfide and othersid e reaction products.

The present-process lis best described "byreference vtothe accompanying drawings. In Figure -1 the charge gas is 'introduced'at vline v,fcontrolled by valve fdfinto coil S of'heatertavhereiit ispreheated to reaction "temperature `or above. Elemental suliur is introducedromsulfur hopper I0 into sulfur melter ZWhere itis meltedlby steam `in coil lll. Heat is appliedto coil ift-so that the `moltensu'lfur is kept at atemperature between approximately 250 'fand 300 F. and preferably about 270 Obviously, those temperatures lare to be avoided at which-viscoussulfurforms. The 4molten sulfur is pumped from the melter Vi2 by means of sub-merged centrifugalpump VT5, lsuit- `able forhandling molten'sulfunthrough'lines f'l' `and 2U into coil 22 Aoi" heater 8. lSufficient pressure must 'be used to force the Vmolten, sulfur 'through coil 22. For this Upurpose, pressures "up to 100 pounds per square-inch-ma-y be used. The ypressures 4under 'which the molten sulfuris moved throughout the system will Idepend `upon `'the 'operation pressuremaintainedin the reactor, Turnaces, and converters.

That portion of the equipment Whichis in 'contact With sulfur-bearingvapors at elevatecl"tern vperatures is `cest constructed vof a materialwhich -is 'resistant "to the corrosive action lof sulfur. Various stainless 'steel alloys, such as those -ofl high `chromium content, Vand 4cliromiuzneniclcel stainless steels stabilized ywith molybdenum, etc.

Other materials 'of con- In coil 22 of heater t, the molten sulfur is heated to a sufficiently high temperature to vaporize it, as for example, 850 to 12%o F. under given operating pressures. Preheated charge gas leaves coil S by line 24, controlled by valve 25, and passes to line 225 Where it joins and uidizes the agglomerating or catalytic material before entering reactor 3E). Sulfur vapors proceed from coil 22 via line 32, controlled by valve 34, to join the charge gas before it enters line 28. Simultaneous intro'ductionef ythe reactants finto .Contact with "each other and "into contact with the agglomerating material bei-ore their entrance into the re- -'actor is generally the preferred technique. How- -even ins-ome cases, especially where higher hy- -idrocarbons are being used as the charge stock, it maybe preferable to introduce the sulfur vapor y'.to'f.theireac'tor separately. In this case, the sulfur vapors pass 41Vfrom line 32 to line St, controlled by -valve38,.intoreactor 3&3 where they meet the hy- 'drocarbonggas and "fluidized material. Both the 4icuteheatecl rchar-.ge :gas and the vapor-ized sulfur may be subjected to superheating to reaction temperatures or above prior to their entry into re.-

" actor 30.

'Reactor 3B is providedmvith a bottom conical shaped section it!) yirivvhich the Ya'dmixture.sofipreheated sulfur vapors vand:chargefgas takes'place. A vertical return .sta'ndpipe'iz lprovided with-.valve 44 for controlling the flow of iluidized :mixture therein is located vwithin Lthe centralportion of reactor '30. Standpipe i 2 extends `from lower conical section F493 yto upper enlarged conical section 46. Make-up agglomerating 'material is introducedinto'thesystem iromhopper fgcoutrolledby valve 5.5,into line T23 whichf'eeds *directly into'lower conical'secti'on 13D oi reactorll via line 52, controlled"by1valve`54- fUnderfeertain conditions, itV maybe desirable to vutilize'tlfle latent heat content of the regenerated agglomerating material to aid in the lvaporization and 'superheating ofthe sulfur; "forthis purpose, the'fhvdrocarbon chargegasheated orunhe'ate'd, passes via lines 24 or 56 into line 28 Where'iluidiza'tion o'f the agglomerating material-takes place. The iiuidized mixture passes 'from line 28 fv'ia fline "58 'and valve 60 to `jo'infthesulfur stream at a point in coil 22 where :the 'temperature 'iis 'about Athe boiling point 'of sulfur. The heated lmixture leaves Acoil 22 and entersreactor 30 `via lines 32 fand F35.

'Contact of the agglorneratingfmaterial with the reactants takes place in'reactor Si@ in the same manner as is employedin'the'moving bed, pebio'le and v'llhermofor cracking processes, Standpipe 42 serves'to vcontrol the'llow of heavier-particles through the iiuidized mass. Conical section '46 is designed 'so that the maximumhindered settling takes place therein.

Accordingly, reaction vproducts and Athe fine portion or smallerparticles of ,agglomeratingfma terial rise to the-small upper section 62Sfor passage into .cyclone separator 264.. `Cyclone .separator 6.4 .serves to .separate .the line particles -of agglomerating material rom the reactionproducts and return them into zthe denser-phase .of the reaction. Reaction products leave the'top vof reactor 3G vialineii to )pass 4:to the carbon disulnde-hydrogen suldefseparation vsystem yto .be kdescribed in Figure 5.2. The vreaction products may contain considerable amounts 4ofinesulfur particles and isome naggloinerating material. This A-inay be removed .(in apparatus notshown) by subjecting the product :stream Vto .countercurrent contact 'with cold :Waterfollowed by 'mechanical separation of the sulfur and agglomerating maiterial, which is returned to regenerator 68.

Heavier particles of agglomerating material leave the reactor 30 by line 10, controlled by valve 12, to enter the bottom of regenerator 08. 'Regenerator E3 may be an ordinary furnace type re# generator for oxidizing theI agglomerating materialtoiree it 'fromocclude'd tars, polymersrand sulfur-containing productsf The principalfproducts of this oxidation'willb'e sulfur dioxide, carbon dioxide, carbon monoxide, and water. yRegenerator 68, as shownin Figure l, is a fluid type regenerator whereinvthe oxidizing gas isY introduced at line 1d. Burning .of vthe agglomerating material takes place throughout the central portion of regenerator 68, andthe regenerated material is caught in the annular space defined by inner cylinder I6 and the outer wall of the. re`A generator for return via! lines 'I8 and 28 `to the reactor 30. The cycle of agglomeratingmaterial from the reactor into the regenerator and back into the reactor is continuous and conditions are maintained for complete -fluidization throughout the system. i f y Gaseous oxidation'products' from regenerator 68 pass through line 80', controlled by valve 82, to catalytic converter 84 for the next step in the operation comprising the recovery of sulfur therefrom. On 'a molar'basis, for each mole of hydrocarbon gas reacting with four moles of sulfur,

there are produced one mole of carbon disulfide anl two moles of hydrogen sulfide. One mole of sulfur dioxide will be required to convert the two moles of hydrogen sulfide tofree sulfur. Since from the carbon disulfide reaction there will be produced in the form of tars and polymers ad- -mixed with unreactedlsulfur, an amount up to about 0.5 mole of sulfur, in combined and uncom-l bined form, which will yield an equivalent number of moles of sulfur dioxide in the regenerator, there will ybe an excessof hydrogen sulfide to be oxidized by the sulfur dioxide. Consequently, a portion of the hydrogen sulfide ranging from onetenth to one-third is oxidized to form additional sulfur dioxide Vforthe reaction. For. this purpose, hydrogen sulfide from the separation system (described in Figure 2) is conducted through line 88, controlled: by valve. 88, toY fure nace 90 wherein it is` oxidized to sulfur' dioxide. exothermic, and advantage is taken offthisto preheat the incoming hydrogen sulde and air within the furnace itself. Furnace 90 may be packed with high temperature fire brick. Preheating the entire furnace by burning natural gas therein may be necessary in; order to bring it to operating temperature before the reactants are introduced. By-pass line92 is Vprovided to con. duct the balance of hydrogen sulfide .to the catalytic converter 84. The mixture of sulfur dioxide and water formed in furnace 00 is conveyed by line 94 to waste heat boiler 85 wherein they are cooled before passage to catalytic converter 84 by line 98, controlled by valve |08.

kThe final step in the sulfur recovery comprises complete reaction of the sulfur Ydioxide content from theregenerator 68 and furnace 90A with the balance of hydrogen sulde to form elemental sulfur. This is accomplished by means of catalytic converter -84 where in the reactant gases pass downward through catalyst bed |02. The catalystfor this purpose may be coarse Porof4 cel, a-highfiron activated bauxite which is-sup'.-

ported onv a stainless steel screen r'estingon -al cast; iron grate..y Normally vthe ,operating condie' The reaction taking place in furnace 90 is i tions within converter 84 are from 500 to 750 F. The reaction may be caused to take place in one or more stages. For example, the first stage may be maintained at about 750 F. vand the second stage at about 500 F. If necessary, heat maybe applied to the reactor in order to initiate the reaction. The conditions Within converter 84 are subject to some variation as long as the complete oxidation of the sulfur takes place.

vEffluent gaseous products from the converter are admitted at the bottom of sulfurv wash tower |04 by means of line I 05. Sulfur wash tower |04 is provided with a mistseparating section |08 and a suitable contact area I I0. Within the tower the gases are subjected to countercurrent contact with a stream of molten sulfur conveyed from sulfur melter I2 vialines I8, H2, and II4 through spray I I6. bottom of sulfur wash tower and any heat absorbed from the hot gases or from the cont Pump |20 serves to recycle molten sulfur to spray I I6 when sufiicient sulfur has accumulated in the bottom of tower I 04. When the process has reached this point, the recycling of sulfur through line II 2 may be discontinued. Excess sulfur is withdrawn through line |22 and passed to `flash drum |24. Flash drum |24 eliminates the'occupational hazard in sulfur melter I2 due to absorbed hydrogen sulfide by flashing it off at atmospheric pressure. f The sulfur within flash drum |24 is returned to sulfur melter I2 by line Referring now to Figure 2, the carbon disulfide separation system, reaction products enter through line 280 into the lower portion of absorber 202. The absorber is fitted with Raschig rings or other liquid-gas contacting elements. Absorber 282 is preferably maintained at a pressure of approximately 20 to 50 pounds per square inch gauge in orderyto absorb carbon disulfide from the reaction product gases. Lean oil is pumped into the top ofV the absorber from accumulator 204 through line 208 by means of pump 2id. As absorber oil, heptane, or petroleum naphtha having a boiling range of about 250 to 400 F. or other fraction boiling above the boiling point of carbon disulfide may be used. Other solvents or absorbing mediums such as benzene and o-dichlorobenzene may be used. It is preferable to choose an absorber oil which has a boiling point or boiling range not too far 'above the boiling point of carbon disulfide in order to enable the latter to be readily stripped therefrom. However, heavier absorption oils may be used and stripping carried out with the aid of a stripping medium suchv as steam, methane, or other inert gas. The unabsorbed gasleaves the top of the absorber through line 2|2 and passes to furnace 98 and catalytic cone verter 84 of Figure l. This gas is composed of hydrogen sulfide with a small amount of hydrocarbon gas and about 0.5 per cent'or less of carbon disulfide. The rich oil is withdrawn from the bottom of absorber 202 by means of pump 2I4, passed through steam heater 256 where the rich oil is preheated to a suitable temperature, as, for example, 208 to 350 F., and charged to the middle section of stripper 2i8. Stripper 2I8 is provided with Raschig rings 22d or other liquidgasV contact elements. Carbon disulfide is strippedfrom the absorber oil and passed from the top of the stripper through linef222, water cooler 'or condenser224, where the temperature Molten sulfur accumulates inthe .boiler 25S.

is reduced to 31019112- 'or less, to accumulator 22.6.

f'gas and/'or vapor which vremains "uncon- 'densed sleeves, the. accumulator '225 through vline 223 yand is returned to the .inlet of the fahsorber 232 'through line v221B. The stripper 2 i3 preferably 'operated at a pressure slightly above the :pressure in 4the yabsorber .262, as, for example, 25 -to 55 pounds per square inch gauge', .in order to avoid the necessity :of compressing the Y.gas returned ythrough line 228. i

.'Ifhe vabsorber -oil is Withdrawn .from `the plate 230 in 4.the bottomrportion of stripper 2i 8 through line i232 vand lcharged Ato reboiler v234 and thence returned throughline 235 to the section of the stripper below the plate 230. Plate 239 .is provided with V.vapor uptakes 238. Lean absorber oil is withdrawn from the bottom of stripper 2:28 through line `cooled in Watercooler 242 to :a temperature below 106 F., and returned `to accumulator 2534. oil from absorber i2-ii?. can be used to ,partially cool the lean oil from stripper' il?, .by providing a suitableheat exchanger. Fresh absorber liquid. is I'added to :accumulator 294 -as required .through line 2.44.

Liquid carbon .disulfide is Withdrawn from accumulator i226 through line 2th and charged lby means of pump 248 to stabilizer 25d. Aportion of .the'carbon disulde may be pumped through line .252 -to the upper portion of stripper 2i8 as redux. The stabilizer :25d is operated at pressures of 20 pounds per square inch gauge or above,1and,preferably inthe ranges of 5) to -150 pounds. The temperature in the bottom of the stabilizer is that needed to eiiectivel-y boil the carbon disulfide Iand free it of hydrogen .sulfide and hydrocarbon gas under the conditions of operation. The stabilizer 25B is equipped with contact surfaces 254, such as Raschig rings, with apla'te 253 having vapor uptakes 25B and a re- In the stabilizer 25d, any hydrogen sulfide or hydrocarbon gas absorbed in the carbon disulde is boiled off and passes overhead through line 2&2 through Water cooler 254. A small amount of carbon disulfide passes overhead, is condensed in part in cooler 24,-and collected in accumulator 266. The condensate from accumulator kit@ is returned to the top oi the stabilizer through line 268 by meanssof pump 210. The uncondensed gases and vapors are withdrawn from the accumulator 266 through line 212 and recycled to the inlet `oi .absorber 2il2 .through linell. The bottoms from the stabilizer 25.0 are withdrawn through a pressure control valve 214 .and charged through line 216 with the necessaryheating or cooling, `to the middle portion of fractionating column l2.78 from which the carbon disulhde is .taken overhead through line 28B, condensed in water cooler 282 and collected in accumulator k28A as ,iinished product. Any bottoms, such as absorption oil, which may have passed overhead with thefcarbon disulfide 'from stripper 228 are withdrawn from the bottom o'f the fractionator 2i'8 through line 236. Fractionator 2li? is equipped with contact surn lfaces 238, such as Raschig rings, a separator plate 2.3i) having vapor uptakes 2&2 and a reboiler 2M. Fractionator 218 is preferably operated at atmospheric pressure. The finished carbon disulfide is Withdrawn from the accumulator 284 by means of pump 28E through line 298 to storage. .A portion of the carbon disulfide may he .recirculated through line .3M as .reflux to y.the topof the fractionation-278.

Having thusdescribed `the apparatus useful in it will he apparent that the rich carrying foutfthe invention, attention is now fdirected to the reactants, thefgeneral reaction conditions, :and .the techniques employed in both the thermal andcatalytic aspects Yof lthe invention, in addition to pointing-out `speoiiic 'examples :of the DIOCBSS.

The chargegas of theipresent process will `comprise .anymixtureof hydrocarbons which vcontain :small amounts, that is, borderline amounts, of constituents which fare prone to .form deleterious side reaction products, to larger amountsV of these. constituents. A typical hydrocarbon comprises ya lnatural gas containing in excess of one mo1e,;per cent of C4 and higher molecular weight 4hydrocarbons or jmore than four mole viper cent :of :C3 and higher molecular Weight hydrocarbons. AHeavier gases including propane, -butana :and :even unsaturated .higher molecular weight `hydrocarbons may be used. The agglomerati-ng material, as has been stated, may be either'catalytic or Vnon-catalytic. If the material is non-catalytic, the reaction is conducted kunder substantially Ythermal conditions and the agglomerating material used may'comprise -sintered alumina, silica, fdiatomaceou-s earth, and pumice. Suchxnaterialsshould have :a par ticlesizesuicientto pass through a 100 `to .200 mesh 'screen in order that they vmay be vproperly luidized. If `a moving bed process is used, the pellets may measure from 1/8 inch to %;inch. `In conducting the thermal reaction, the zpurpose of the inert agglomeratingmaterial` is `to "fscavenge the tarry rand .polymer--containing by-produc'ts, and 'vfor this purpose only a relatively small amount of inert material in relation' to'theamount of :Charge reactants Ais znecessary. Generally, the amount .of fagglomerating material will need vto be suicient tozocclude 'all of .the tarry `products inherently :present in the hydrocarbon charge under the'operating conditions employed. Generally, this :amount 'will vary from about dive `.to fifty weightfper cent lbasedfon :the Vtotal yWeight of charge reactants.

`The thermal'freactiontmay be :conductedat from about 842 .to l650 F., lAlthough hydrocarbons higher Yin molecular Weight than .fmethane will react thermally with sulfur vapor :fat'comparatively moderate temperatures, this technique requires long contact tim'esand, asia-consequence, dehydrogenation and :tar'iormation reactions Vare increased relative to that 'of carbon disulhde formation. .Atmore elevated temperatures vWhere the lfrate of .carbon disulfide 'reaction "is rapid, these side'reactions'will 'be minimized `and any previously .dehydrogenate'd products that may have 4`formed `.Willareaot with sulfur to form additional "amounts .of carbon disulde. For these reasons, .the preferred thermal 'reaction'temperaturerangesfromlQSZ" .F.lto '1500" 1F. with adequate residence time within .the reaction .zone for carbon 4disulfide formation. These reaction or residencetimes will vary .according to the temperature .employedand .according to the type of hydrocarbon charge gas used. The preferred reaction times "are in .the order of 0.5 to '25 seconds `under .atmospheric pressure conditions. When higher pressures yare used, vthe reaction times `Will fbe v'relatively increased. Since unsaturated hydrocarbons react'more readily than saturated hydrocarbons, with other factors being equal, .the reaction time for the former will be lessened. l

4Semeral catalyticmaterialsare available which lwill serve .to both vpromote `the lreaction and, when used according to the methods outlined here, will serve to remove deleterious side reaction products. These materials include synthetic silica-alumina, silica gel, fullers earth, bauxite, activated alumina, and in general .thosetypes of clays Ywhich are effective in theiremoval of color bodies and gum-forming bodies from petroleum oils. These catalysts may be used alone or in combination with one oivmore; compounds of metals of groups IV, V, VI, VII, and VIII of the periodic table as promoters. The oxides of zirconium on silica gel or activated carbon are especially eiective catalysts. Oxides of titanium and thorium may likewise be used. In addition, the oxides and sulfides of iron, vanadium, chromium, molybdenum, and manganese may be used as` promoters in combinationv with silica gel, fullers earth, or activated alumina catalysts.

When conducting these reactions catalytically, lower temperatures maybe employed, the preferred range being from 842. F. to 1300YF. For both Athe catalytic and thermal reactions, it is preferred to use about the stoichiometric amount of sulfur needed to react'with `all of the carbon and hydrogen ofthe hydrocarbon to form carbon disulide andk hydrogen sulfide. Theratio of lsulfur to hydrocarbon charge gas may, however,vary considerably and it is preferred to operate with an amount of sulfur between 10 per cent in excess Aof stoichiometric requirements and 110 per cent below stoichiometric requirements.

ployedin pebble heaters and in Thermofor cracking processes. Another procedure 'consists in mixing the agglomerating material to--form ar slurrywithfthe liquidsulfur to be charged to the reactor.- An alternateprocedure comprises fluidizing the agglomerating material with the sulfur vapors at apointafter vaporization and before orduring the super-heating of thesulfur. A preferred feature of the thermal technique is toseparately preheatthe sulfuryapors and hydrocarbon charge gas up toreaction temperatures and then combine these preheated streams immediatelyV prior to their entrance into `thefreaction zone, This procedure overcomes thel de'- hydrogenating effect of hot sulfur yvon the hydrocarbons with subsequent coke formation.

Whether thermal or catalytic; the rreaction conditionsand proportions of reactants may vary somewhat-depending-onthe type `of charge gas employed. Based on reaction conditions of about 1112" F. and atmospheric pressures the weight ratio of agglomerating material to charge-gasmay vary-from. 1:1 -tof20:1 with thepreferred range -being 2:1to 10:1 and thermedian about 5:1. yThis may be based on either a 10 per cent deficiencyor percent excess on stoichiometricity.Y

IIYhe regeneration-of used of sulfur based suspension through a regeneration zone under conditions adapted to cause combustion of the occluded tars andpolymers .1 collected on the sur.-

facethereof. during contact .Withthe reaction mass. The temperature of the regeneration may be controlled by recycling into the regeneration zone a portion of the regenerated agglomerating material after this portion has been cooled toa suitable temperature in aV cooling zone extraneous of the regeneration zone. The quantity of cooled recycled agglomerating material is dependent upon its temperature, and decreases with decrease in temperature of the cooled recycled material stream. Common practice is to withdraw the cooling material stream from the dense phase of the mass Within the regeneration zone, cool it to the desired cooling temperature and recycle it -to the regeneration zone.

It is apparent from the description thus ffar that the method of operation of this invention permits the continuous ecient conversion of higher molecular Weight hydrocarbons into carbon disulfide. By operating in accordance with the invention, these higher hydrocarbons are reacted almost quantitatively to carbon disulfide with continued high catalyst activity throughout the reaction. This isV inherent in the process since the reactants are' continually being contacted with fresh or regenerated agglomerating material under either thermal or catalytic conditions andthe agglomerating material is continuously removing the deleterious side re. action products from contact with the reactants during their combination to .form carbon disulde and from the atmosphere of thexreaction. The sensible heat carried by the regenerated agglcinerating material, when recycled back into the liquid sulfur stream, will aid in the Vaporization of the sulfur 'and its subsequent superheating. The present method also provides an efficient means for the reclamation of the sulfur content of they tar or free sulfur admixed or in solution with the tar for recycling in the'proc'- ess. Lastly, sensibleheat is provided for the reaction itself under endothermic conditions of operation. f

` kThe following examples are given to illustrate the invention:

Example 1.-Substantially pure ethane gas wasL reactedv with, a stoichiometric amount of sulfur vapors at 1112c F. in a fixed bed reactor. Initiaily only a small amount oftar formation was experienced. However. after a few hours, con- 4.version to carbondisulfide had declined from its initial levelof .90 per cent to a value in the order t of pentanes and 0.5 percent hexanes and heavier mospheric pressure intoa reaction zone Jmainktained at a temperature of 1112 F. and fitted.

with a static bed of silicagel catalyst. Employing a stoichiometric ratio of gasand sulfur at a total space velocity of 450 (gas and sulfur (S2) volume calculated at 0 and 760 millimeters of niercurw a conversion of 58 per cent ofthe hydrocarbon gas to carbon disulfide was obtained.-

It was found Aunder these. Iconditions that competing side reactions occurred to such an extent Y that aboutA 2 per cent of the charged gas 're--y acted with the sulfur to yield a viscous tarry polymeric material .and some coke, With the result that a material decrease in over-all eiiiciency and catalytic activity followed. Recovered Vsulfur .was around 40`per cent'of that charged.' An initial high conversion-'of around 76 per cent acca-,69o

ll was attained fora period of about one hour after which conversion dropped gradually and after. about six hours operation, conversion leveled off at about 58 per cent.

Example 3.-A natural gasv containing around 3.0 per cent of C4 hydrocarbons and heavier is passed through a uid reactor using the iluid technique in the presence of the. saine agglomerating material or catalyst as used in Example 2. The reactor. is maintained at 1112o F. under substantially atmospheric pressure conditions. rIvhe sulfur to gas ratio is controlled to approximately stoichiometric requirements. The Weight ratio of catalyst. to natural gas is maintained at about 6:1, and the. contact. time is about ten seconds. The over-all conversion of the hydro carbon. gas over. a period of 12 hours will bev about. 90 per cent. of .which 88 per cent appears. as carbon disulde, and 2 per cent as tar. Ten per cent. of the natural gas remains. unreacted and 'substantially 10 per cent of the. sulfur is unreacted.

From the. above examples, it isseen by employingA the technique ofthe present invention the. .deleterious eiect of side reaction products eliminated andtheoverali reaction efficiency is maintained. atv a high level. Although the invention has been described by specic embodiments, these. are only illustrative and the only limitations. to be placed. on the. invention are found in the. appended claims.

. What is claimed 1. The method of converting hydrocarbons to carbon disuliide by reaction Withzsuli'ur, said hydrocarbons.. `containing constituents tending to form tarry sulfur-containing. by-products, comprising passing preheated hydrocarbons and preheated suliur vaporsv into contact With an agglomerating material in a reaction zone, said agglomerating. material being capable of occluding saidisulurecontaining by-products and-said reaction zone being maintained under conditions to promote. the formation of carbon disulfide and hydrogen sulde, separating said agglomerating material and. the` carbon disuliide and hydrogen sulfide so.` formed, subjecting' said agglomerating material to. an oxidizing atmosphere capable of oxidizing the sulfur contenter said occluded byproducts to. sulfur dioxide, and reacting said sulfur dioxide so. produced Withthe hydrogen sulfide under conditionsV to produce elemental sulur for reusein the reaction.

2. rihe method in accordance withy cla-im 1 inl which the aggl'omerating` material is selected fromy the. group consisting of sintered alumina,Y silica, diatomaceousr earth, silica gel, activated alumina, vactivated clays,- andsilica-alum-ina coin'- positionsi.

3. The. method in. accordance with claim 1- inf whichl the hydrocarbon isselected fromthe group consisting of natural. gas, propane, butane, and their existing olenie homologues and mixtures thereof. Y

`4. rThe method in accordance with' claim 1 in Which the. carbonv disulfide forming reaction isv Which the hydrocarbons. andsulfur are preheated` to reaction temperature.

6. The method in accordance With claim 1v in. Which the sulfur is present in an amount betweenA a4 I0 per cent deficiency anda 10 per cent excess l2 of. stoichiometric requirements. for the reaction;` 7. The method in accordance with claim, 1 in which the oxidation of occluded sulfur-containing by-products on said agglomeratirig material Vis conducted at temperatures in the order. of 800 F. to 1500L7 F.

8. The method in accordance'with claim 1. in which the reactants and agglomerating material aremaintained in a I'luldized state Within the reaction zoneat about 1112 F; under s'ubstantlally; atmospheric pressure with the ratio or' agglomerating material to hydrocarbon being mains tained at about 6:1 with a contact time of about 10 seconds.

9. ille method inv accordance with claim l in Whiclithe sulrur dioxide and hydrogen sulfide. are reacted at temperatures Irom 500 F. to 150 F. in the presence or a catalyst capable oi' promoting the ioi'mation oi' elemental suliur;

10. The method or continuously producing carbon disulfide by reaction or hydrocarbons and sul'iur, said hydrocarbons containing substantial amounts 0I constituents tending to iorm dele-- terious tarry suliur-containing by-products comm pi'isillg, contacting preheated nydl'ocarbonsv and preheated suliur vapors with an agglomerating. material in a reaction zone under conditions capable ol tlieiormation oi carbon usuliide and hydrogen sulfide;4 said agglomerating material being, capable 0Iv occludlngv said, Sulrurf-containing byproducts, sepa-rating carbondisul1ide hydrogen sulfide, and said agglomerating material iroin. eacii other, subgecting saidagglomeratlng, ma.- terial to an oxidizing atmosphere capable 01 producing sullur dioxide :rom said occluded by-4 products, reacting. said suliur dioxide and said Spaiated hydrogen sliliide under conditions ca.- pable or forming elemental sulfur.

il. 'The method in accordance with vclaim 10- in which the agglom'erating matei'ialisv selected rrom tile group consisting o1 sintered alumina, silica,y diatoiiiaceousv eartn, ,sillca gel; activated.

alumina', activated clays, and silica-alumina coinpositions. v f l Y l Y iz. 'i ne-method,in accordance with claim 10 in which the hydrocarbonisselectedrroin the group consisting 0I' natural gas, propane, butane,` and their existing olennic homologues. and mixtures thereof. l

13.. ',Lhemethod in accordancerwith claim 10 in which the carbon. disulfide vIorining reaction is.

conducted ata temperature betweenwabout 842 l?. and 1500u Fi, and the ratio of agglomerating, the. range of 2:1.

" tween av lo. per cent ld .en'ciencyand a ll) per cent excess of stolchiometric requirements for the reaction lo. VThe method of converting hydrocarbons to carbon disulfide-by reaction with sulfur, said h ydrocarbons containing' constituents tending to formtarry suliur-containlng by-pioducts,l y coinpiising passing preheated hydrocarbons and pre heated sulfur vapors into contact Withan agglolneratlng; materialin areaction zone, said aggloinei'ating material being capable of occluding saidsuliurscontaining by.products and saidreaction zone being maintained. `under conditions to.

promote the iormation` of carbon disulfide and hydrogen suliide,A separating said. agglomeratingY `References Cited in the le of this patent Number UNITED STATES PATENTS Name Date De Simo Jan. 16, 1940 Thacker Oct. 5, 1943 Odell et al. Nov. 27, 1945 Ferguson Aug. 30, 1949 Belchetz Nov. 8, 1949 Holder Nov, 14, 1950 Gamson June 12, 1951 

1. THE METHOD OF CONVERTING HYDROCARBONS TO CARBON DISULFIDE BY REACTION WITH SULFUR, SAID HYDROCARBONS CONTAINING CONSTITUENTS TENDING TO FORM TARRY SULFUR-CONTAINING BY-PRODUCTS, COMPRISING PASSING PREHEATED HYDROCARBONS AND PREHEATED SULFUR VAPORS INTO CONTACT WITH AN AGGLOMERATING MATERIAL IN A REACTION ZONE, SAID AGGLOMERATING MATERIAL BEING CAPABLE OF OCCLUDING SAID SULFUR-CONTAINING BY-PRODUCTS AND SAID REACTION ZONE BEING MAINTAINED UNDER CONDITIONS TO PROMOTE THE FORMATION OF CARBON DISULFIDE AND HYDROGEN SULFIDE, SEPARATING SAID AGGLOMERATING MATERIAL AND THE CARBON DISULFIDE AND HYDROGEN SULFIDE SO FORMED, SUBJECTING SAID AGGLOMERATING MATERIAL TO AN OXIDIZING ATMOSPHERE CAPABLE OF OXIDIZING THE SULFUR CONTENT OF SAID OCCLUDED BYPRODUCTS TO SULFUR DIOXIDE, AND REACTING SAID SULFUR DIOXIDE SO PRODUCED WITH THE HYDROGEN SULFIDE UNDER CONDITIONS TO PRODUCE ELEMENTAL SULFUR FOR REUSE IN THE REACTION. 